Resin



June 24, 1941. M GE|GER HAL 2,247,154

RESIN v Filed April 25, 193s Vinyl/fa AYAF Resin M. ATTORNEYS.

Patented June 24, 1941 RESIN Lyle Geiger, Grafton, and William D.Johnston, Jr., Avalon, Pa., assignors to The Neville Company,Pittsburgh, Pa., a corporation of Pennsylvania Application April 25,1938, Serial No. 203,980

4 Claims.

This invention relates to improvements in blending vinyl acetatepolymers with other resinous bodies through the use of phenol-modifledcoumarone resins.

It is among the objects of the invention to provide resin compositionscombining satisfactory thermoplastic properties with unusual toughnessand elasticity.

Another object is to provide blends of vinyl acetate polymer and resinsnormally incompatible therewith, by the use of phenol-modified coumaroneresin.

A specific object is to provide compositions containing coumarone resinand polymerized vinyl acetate, which are homogeneous and possessphysical properties which render them desirable in the arts.

A further object is to provide a method of making compositions of thetypes referred to.

Other objects will appear from the following description.

The so-called coumarone resins are produced by polymerization of certainconstituents of crude solvent naphtha produced in the by-product cokingof coal. The polymerizable constituents of such naphthas are commonlycoumarone and indeneand their homologs, which are present in amounts andproportions which depend upon the proximate source from which thenaphthas are derived as well as upon the operating conditions by whichthe naphthas are produced. Such naphthas may containalso otherpolymerizable constituents, such as dicyclopentadiene.

Depending upon such factors as well as upon.

treatments of the naphtha to fractionate the polymerizable constituentsmore or less completely, the polymers produced may thus comprisepredominantly polycoumarone or polyinalkalies coupled with theirthermoplastic nature provides a combination of properties desirable-inmolding plastics. These resins have not found extensive application forsuch purposes,

however, because of their inherent brittleness and low strength, and upto the time 01' this invention plasticizing, or tempering, of thecoumarone resins to adapt them to thermoplastic molding has not beenachieved in a completely satisfactory manner. For instance, somematerials must be used in large amounts to provide the necessarytoughness and strength, while the properties of others are such that themixtures do not provide to the fullest extent the desirable propertiesof the coumarone resin. The vinyl acetate polymers possess propertiessuch that, other things being equal, they might be compounded withcoumarone resin without detriment to its desirable properties, but ithas not heretofore been possible to use them with ordinary coumaroneresins of commerce because the two are incompatible.

We have discovered, and it is upon this that our invention is predicatedin part, that phenolmodified coumarone resins are, incontrast withordinary coumarone resins, highly compatible with vinyl acetate polymerswith production of homogeneous thermoplastic compositions of unusualtoughness and elasticity, and-that very small amounts of the vinylacetate polymer suftlce for the purposes of the-invention. 'The hardergrades of phenol-modiiledcoumaroneresins are similar to ordinaryjorunmodified, coumarone resins to the extent that they 'are'highly brittledene, or mixtures of both, or polymers of the other polymerizableconstituents alluded to.

crude solvent naphtha are considered as being mixtures of coumarone andindene polymers.

polymers.

and of low'strengthybut ior some reasonnot fully apparent, the phenolicinvolvement of the former confers compatibilityiwith vinyl acetatePhenol-modified coumarone resins are those produced fromthelpolymrizable constituents of crude solvent naphtha bypolymerizationwith "concurrentinvolvement with a phenolic body.

For brevity reference will be made herein to coumarone resin but fromwhat has been said it will be understood that the term contem--'-Various procedures are available for the production ofsucnphenol-modified coumarone resins, such as that described in GermanPatent No'.

1302,5213. An improved procedure is disclosed in Patent'Nci. 2,077,009,granted April 13, 1937, to

Joseph Rivkimin accordance with which phenolmodifled coumarone resin isproduced by efl'ecting the polymerization, in the presence of a phenolicbod such as cresols, phenols, naphthas, and the like, which is reactivewith the .polymerizable constituents in the naphtha, by

means of activated clay and with moderately elevated temperatures, forinstance, in the neighborhood of 100 C., the reaction body beingagitated during the course of the reaction.

Still another improved procedure for the production of phenol-modifiedcoumarone resin is described in application for United States LettersPatent Serial No. 89,847, flled July 9, 1936, by

' Joseph Rivkin. As disclosed therein, the phenolic involvement isachieved through the conjoint use of a sulfuric acid base catalyst and aphenolic reagent in a quantity by weight not less than about 22 per centof the weight of the polymerizable constituents of the crude solventnaphtha. During the progress of the reaction the reacted body isagitated and its temperature is maintained below about 60 C., mostsuitably within the range 25 to 35 C. The term sulfuric acid basecatalyst is used in this instance to refer concisely to concentratedsulfuric acid or derivatives thereof obtained by the substitution of atleast one hydrogen atom or one hydroxyl group of the sulfuric acid by analiphatic or an aromatic group which may, in turn, be substituted byother groups, such as hydroxyl groups, amine groups, and the like. Thislatter procedure results, in general, in products having a lower theblend does not enableone having no knowledge of its constituents tojudge their presence.

Smaller amounts than those stated might be used but generally a minimumof about 5 per cent of vinyl acetate polymer is needed to confer goodtoughness and strength. Larger amounts may be used, but partly forreasons of economy it is desirable in general to use not more than about50 per cent of vinyl acetate polymer.

Such mixes are suitably thermoplastic, tough and strong for moldingpurposes. The melting point of the phenol-modified coumarone resin isgenerally raised. This is indicated by, for example, a blend of 90 percent of phenol-modified coumarone resin of 86? C. melting point sold as"Nevi1lac by The Neville Company, of Pittsburgh, Pennsylvania, and 10per cent of a vinyl acid number than characterizes the phenol-modheavyoil by analogy to the similar heavy oil produced through fractionationof the product of ordinary' polymerization of the reactive bodies incrude solvent naphtha. Both fractions are phenolically modified, andboth may be used in the practice oi. the present invention.

We have discovered furthermore that not only is phenol-modifiedcoumarone resin itself satisfactorily compatible with vinyl acetatepolymers, but also that such binary compositions are capable of blendingcompatibly with resins incompatible with vinyl acetate polymers butcompatible with phenol-modified coumarone resin, with production ofthree-component blends having desirable properties. In other words,resins incompatible with vinyl acetate polymers but compatible withphenol-modified coumarone resins. are compatibly blendable with the twoto provide three-component blends, and although the three components may(not in each instance be compatible in all proportions the range ofcompatibility and the properties of the blends are such' as to becommercially desirable, especially becausev it is thereby possible tocompound vinyl acetate polymers with resins that could not be usedsatisfactorily therewith heretofore. For instance, it is possible inthis manner to compound ordinary coumarone resin with vinyl acetatepolymers which, so far as we are aware, has not been accomplishedheretofore.

Referring first to the simple blending of phenol-modified coumaroneresin with vinyl acetate polymer, very small amounts of the lattersuiflce to effect radical changes in the characteristics of the former.In fact, mixes of phenol-modified coumarone resin with as little as 5 to10 per cent of vinyl acetate polymer possess physical properties sodifferent from those of the individual materials that observation ofacetate polymer sold by Carbide 8: Carbon Chemicals Corporation asVinylite grade AYAF. The resultant mix had a melting point of 103 C.Again, a mixture of equal parts of the same phenol-modified resin andthe same grade of "Vinylite" could not be melted; this compositionsoftened at high temperatures, about C., to the extent that it could bemolded under pressure, and it was extremely hard, devoid of brittlenessand of great strength for such materials. Such compositions are of greatutility as molding powders.

As stated hereinabove, we have discovered further that the use ofphenol-modified coumarone resin makesit possible to produce compatiblethree-component blends of vinyl acetate polymer and resins compatiblewith the former but not with the latter material. As exemplifying thisaspect of the-invention, reference may be made to blends made fromphenol-modified coumarone resin, Vinylite AYAF, and various other resinswhich are not alone compatible with "Vinylite AYAF. In these tests therewas made up a base mix of nine parts of phenol-modified coumarone resinand one part of the stated vinyl acetate polymer, and to portions ofthis base mix there were added progressively increasing amounts of thethird component to ascertain the limits of compatibility of the latter.The solubflizing action of phenol-modified coumarone resin upon thesemutually incompatible mate- Similar results are attainable with otherresins compatible with the phenol-modified coumarone resin but notcompatible with the vinyl acetate polymers. Thus, this has beendemonstrated with, for example, Resoglaz, a polystyrene resin sold byAdvance Solvents and Chemical 00.; Ethocel" 18-V, an ethyl cellulosesold by Dow Chemical Co.; Tomesit 125-V, a chlorinated rubber sold byHercules Powder Co.; Uformite F-224, an urea-formaldehyde resin sold byThe Resinous Products 8: Chemical Co., Inc., hydrogenated Monsanto"Petroleum Resin," and "Nuba No. 1 resin sold by The Neville Company.The lastnamed material is a coumarone resin produced from the stillresidue remaining after fractionation of light oils originatingand-recovered in the by-product coking of coal. The residue is a mixtureof resins and oils, and by steam distillation to remove oils there isrecovered a solid resin of sulfonated nature and comprising chieflycoumarone resin. As showing its compatibility with vinyl acetate polymerthrough the practice of this invention. tests have shown that as much as63 per cent of such "Nuba resin, No. 1 grade, is compatible with 33.3per cent of Nevillac and 3.7 per cent of "Vinylite AYAF.

This aspect of the invention is exemplified particularly well by theblending of ordinary coumarone resin with vinyl acetate polymer. use ofphenol-modified coumarone resin in accordance with the invention it ispossible to provide homogeneous blends containing very large amounts ofordinary coumarone resin through the use of very small amounts of vinylacetate polymer, while attaining desirable plastic and physicalproperties. For instance, as little as 2 to 10 per cent of vinyl acetatepolymer suffices for the purposes of the invention; larger amounts mightbe used, of course, if desired. The following table shows the resultsobtained with two widely varying grades of coumarone-indene resin madeby The Neville Company, of Pittsburgh,

, Pennsylvania, the tests being conducted in the manner described inconnection with the foregoing table:

Coumarone resin-unmodified Nevillao" Vinylite" Maximum percent com-Grade patible Percent Percent 37.5 4.2 58.3 R63 (M. P. over 150 18.0 2.080.0 a-zb'nu. P. as" 0.

The accompanying graph illustrates this further with reference to thecompatibility of the R-29 grade coumarone shown in the foregoing.opacity developed upon evaporation of the solvent, the proportions weretaken as being incompatible. In the triangular graph field A repre- 5sents the compatible proportions of this tri-component system, and theability of the phenolmodified coumarone resin in producing compatibleblends is evidenced by the fact that this field encompassesapproximately 65 per cent of all possible combinations of these threeconstituents.

In the foregoing tests there were used hard grades of phenol-modifiedresin. The invention coumarone-indene resin,-

By the is applicable also to the use of the softer grades, such asphenolic heavy oil, as referred to hereinabove. As exemplifying this,one blend that has been made contained 3.6 per cent of "Vinyl- I ite,"32.2 per cent of phenolic heavy oil, and 64.2

per cent of a coumarone-indene resin containing about per cent of indenepolymer and having a melting point in excess of C.

Three methods are in general use for the compounding, or blending, ofresin compositions. One involves the use of a common solvent, or theblending of two or more resin solutions. The second resides in millingthe resins together in a suitable device, thus producing merelymechanical homogenization. The third consists in melting one or more ofthe resins together with agitation in the molten state to bring aboutsolution or blending. This latter method is, in general, desirablebecause it eliminates the use of volatile solvents together with theresultantly necessary solvent recovery systems, and the fire andexplosion hazards which attend the use of the first procedure;furthermore, it eliminates the rather considerable power costs which maybe involved in the application of the second procedure. The fusionmethod is simple and requires merely a source of heat and means formechanical agitation, with minimum power consumption.

While in the practice of the invention the materials may be blended invarious ways for certain purposes, or within certain proportions, wehave discovered that infollowing the third of the foregoing procedures,the best results are to be had by first melting the phenol-modifiedcoumarone resin, adding to the melt the vinyl acetate polymer andagitating until solution of the latter in the former is complete, andthen-adding the unmodified coumarone resin. In this manner it ispossible to produce much higher ratios of ordinary coumarone resin incompatible solution than with other orders of mixing the threeingredients. Also, the production of homogeneous blends is greatlyaccelerated as compared with other orders of mixing the three materials.

It is understood that "Vinylitef AYAF is a polymer of vinyl acetate. Theparticular grade used had a viscosity of 15 centipoises. However, theinvention is applicable to other vinyl acetate polymers, such as thoseof different viscosity, and thus 01' diil'erent degree ofpolymerization, and others. data obtained by actual tests:

'Shawinlgan Products 0011)., New York, N. Y.

It will be observed that despite wide variations in the viscosity of theVinylite used, the compatibility was not disturbed. Also, the samecompatibility was observed with the "Gelva resin, which is supposed tobe a vinyl acetate polymer similar in character to Vinylite.

These results serve to illustrate the mutual solubilization whichcharacterizes the present inven- This is evidenced by the following tionregardless of the origin, type or viscosity of the vinyl acetatepolymer.

Moreover, in the investigations of the tricomponent' systems referred toabove, the characteristics and physical properties of the blends wereclosely alike as far as could bedetermined. Particularly, thecompositions showed great strength and lack of brittleness even thoughthe vinyl acetate polymer content was less than 5 per cent of the totalcomposition.

According to the provisions of the patent statutes, we have explainedthe principle of our in vention and have described what we now considerto represent its best embodiment. However, we desire to have itunderstood that, within the scope of the appended claims, the inventionmay be practiced otherwise than as specifically described.

We claim:

1. That method of compounding synthetic resin composition comprisingpreparing a melt of resin formed from the polymerizable constituents ofcrude solvent naphtha and produced by polymerization and concurrentphenolic involvement with a phenolic body, adding vinyl acetate polymerto the molten resin, then adding resin compatible with said phenolicallyinvolved polymer but incompatible with said vinyl acetate polymer, andagitating to produce homogeneity of the melt.

2. That method of compounding synthetic resin composition comprisingmelting phenolmodified coumarone resin, adding vinyl acetate polymer tothe molten resin, then adding resin compatible with said phenolicallyinvolved polymer but incompatible with said vinyl acetate polymer, andagitating to produce homogeneity of the melt, said vinyl acetate polymerconstituting at least about 1- per cent of the composition.

3. A method according to claim 2, said resin incompatible with vinylacetate polymer being cyclopentadiene resin.

4. A method according to claim 2, said resin incompatible with vinylacetate polymer being alkyd resin.

LYLE M. GEIGER. WILLIAM D. JOHNSTON,'JR.

